Thiophosphonic acid derivatives and method of preparing the same



Patented Mar. 16, 1954 :SEHIOPHOSPHONIC ACID DERIVATIVES AND METHOD OF PREPARING THE SAME Iiulx, New Brunswick, and Richard L. "sheparmsomerville. N. J assignors to Am'er- Dany, New York, N. Y., a

corpiiratioii' of Maine No Drawing. Application January 8, 1952, Serial No. 265,544

6 Claims. (Cl.- 26032 39) 1 This lnv ei'ltion relatesf to the preparation of new organic compounds. More'fparticularlyg it relates to" '-thiopho'sphofiic"'-.acid -=dia-inides and methods for their preparation.

" in which X is halogen and R and-R. :areasr defined above. The ethylenimine xcompoundirnay be; for example, 'ethylenimine itself or 'a iC-substituted ethylenimine such as Z-methylethylen- The ethyl- The N,N'-diethylenbenzene Certain diamidesi of phosphonic acids have 5 imine; Z-ethylethylenimine; 2,2-dimethylethylbeen described in the literature. enimine; 2-propylethylenimine; 2,2-diethylethyl- The compounds of the present invention, in enimine; Z-hexylethylenimine; etc. contrast to those of the prior art, are N,N-dienimine intermediates may be prepared by known alkylenimides of thiophosphonic acids which may procedures such as treatment with sodium hybe illustrated by the following general formula: 10 droxide of the corresponding 2-haloethy1amines or of the sulfuric esters of the corresponding Z-hydroxyethylamines. i ;l* The reaction to prepare the compound-of the '0 present invention is preferably carried outirr an inert organic solvent for example, .benzene, ;eth'er, S=P dioxane or ethylene dichloride. -;It is necessary /CH2 to have present as an acid acceptor a tertiary "N, R amine, for example; -triethylamine or pyridine. With the more stable thiophosphonic chlorides the reaction can also be carried out in aqueous R solution and under .these circumstances, the acid 4n:which R isrselected:iromithegrou of hydroa p may be an alkaline substance Such as gen; a radical of ather aliphatic, ali h t c-aroan alkali metal hydroxide or carbonate or bicarmatic, cycloaliphatic series, and R is'xselected bonate- Isolation of the p du t m a i irom'the group of radicals of the-.-aliphatic,cyclodiu may b mpl by tlfal i it ra-liphatic, aliphatic-aromatic,xheterotyclic and tertiary amine vll'yd'lbllaliliie' S aHi QQ Q aromatigsefies, I from the organic solvent or by evaporation"of I --.Comp,ounds of the present invention-because the Organic fi fip p in aqueous of-theareactive ethylenimine groupsrare also usedium, m m r ma be lat d y di t m1 as new t t chemicals. and-{maybe 1 filtration. Others must be extracted from the merized t form newirplasijicg aqueous medium with an organic solvent and The e m d f th ti are prepared subsequent evaporation of the organic solvent. by starting with a thiophosphonyl dichloride or The procedure willvary with the individual memmm- {for sz xa -l i'thafithiophosphonyl hers according to their solubility properties. dichloride; beta chloroethanethiophosphonyl =di- The reaction is generally c ried out at a temc'hmrid butanethiophosphonyl i mb l cyperature within the range of 0 C. to about 80 C. clohexanethiophosphonyl dichloride; 3 benzene- At this temperature range the acti n is generthiophosphonyl dichloride; '4 methylbenzeneally. complete Within a period of severaljminutes thiophosphonyl dichloride; 2-chlorobenzenethiofi v I k phosphonyl d m n knalohthalenethiwhos- 40 The following example illustrates the'preparaphonyl di hl id or 2-thjophenethjophosphony1 tion of representative thiophosphonamides of the dichloride. These thiophosphonyl dihalides are present invention All parts are by Weight unless reacted with two molecular equivalents of an Otherwise indicatedethylenimine compound which may contain one or more substituents on a ring carbon atom to Example produce the desired compound. This latter reaction may be illustrated by the following equa To a solution of z0.2 parts of triethylamine, 8.6 on: parts of ethylemmme in 125 parts of benzene is added with agitation, a solution of 21.1 parts of benzenethiophosphonyl dichloride in 45 parts of N R benzene at 5-l5 C. over a period of one and onehalf hours. The reaction mixture is kept at room (X)2 R temperature for an additional two hours and the triethylamine hydrochloride is filtered off. Most T\ mm of the benzene is removed from the filtrate under R reduced pressure.

R phosphondiamide, crystallized from petroleum ether, is obtained in small white crystals, melt- R ing point 102.5-103.5 C.

- 3 We claim: 1. Compounds of the group having the general formula:

in which R is a member of the group consisting of hydrogen and lower alkyl radicals and R is a member of the group consisting of lower alkyl, phenyl, lower alkylphenyl, chlorophenyl and naphthyl radicals.

2. Compounds of the group having the general formula:

in which R is a monocyclic aryl radical containing not more than eight carbon atoms.

3. N,N' diethylene benzenethiophosphondiamide having the formula:

4. A method of preparing compounds having the formula:

NQ R

in which R is a member of the group consisting 55 of hydrogen and lower alkyl radicals and R is a member of the group consisting of lower alkyl, phenyl, lower alkylphenyl, chlorophenyl and naphthyl radicals which comprises reacting a compound having the formula:

(X): s=r

R! in which X is halogen of the atomic number between 17 and 35 and R is as defined above with a compound having the formula:

l CH: HN\ /R in which R is as defined above, and recovering said compound therefrom.

5. A method of preparing compounds having the formula:

in which R is a monocyclic aryl radical containing not more than eight carbon atoms which comprises reacting a compound having the formula:

References Cited in the file of this patent Michaelis et a1., Ber. Deut. Chem., vol. 31, p. 1042 (1898).

Miohaelis, Liebigs Ann., vol. 326, p. 129 (1903). 

1. COMPOUNDS OF THE GROUP HAVING THE GENERAL FORMULA: 